Photopolymerizable oligomer

ABSTRACT

Ethylenically unsaturated polymerizable oligomers, which are particularly useful in printing plate compositions, comprise backbones formed by the removal of hydrogen from hydroxyl groups and having bonded thereto both carboxylic acid groups and ethylenically unsaturated, free radical polymerizable groups, these last two groups bonded to the backbone through the reaction of isocyanate groups.

This is a division of application Ser. No. 15,586 filed Feb. 27, 1979,now U.S. Pat. No. 4,228,232, which in turn is a continuation-in-part ofapplication Ser. No. 901,480, filed May 1, 1978, now abandoned.

FIELD OF THE INVENTION

This invention relates to novel photopolymerizable compositions,photoimagable recording elements, and a process for imaging withphotopolymerizable compositions.

PRIOR ART

Photopolymerizable compositions have been used in photosensitiveelements, such as printing plates, for a number of years. Suchcompositions have been satisfactory only where contact printing of theplate and relatively long time exposures can be tolerated. Mostrepresentative of the prior art are compositions disclosed in U.S. Pat.Nos. 3,218,167 and 3,887,450. In U.S. Pat. No. 3,218,167, photosensitivecompositions comprising (1) an ethylenically unsaturated compound (e.g.,pentaerythritol polyacrylate), (2) a sensitizing dye, and (3) athermoplastic binder (e.g., cellulose ether or polyvinyl ether). In U.S.Pat. No. 3,887,450 a radiation sensitive composition is described whichcomprises (1) an acrylic monomer (e.g., pentaerythritol triacrylate),(2) a photosensitive dye, and (3) a binder comprising a copolymer ofstyrene and a carboxyl containing comonomer (e.g., acrylic or maleicacid). This latter composition has the advantage of being developable(i.e. soluble in non-irradiated areas) by basic developers. Thecomposition is relatively slow, however, and must be exposed in theabsence of oxygen.

Radiation sensitive elements which are oxygen insensitive have beenproduced by overcoating the elements with an oxygen barrier layer as inU.S. Pat. No. 3,895,949. Here a support bearing a photopolymerizablecomposition comprising a glycidyl acrylate adduct of a styrene/maleicanhydride adduct, an ethylenically unsaturated monomer (e.g.,pentaerythritol tetraacrylate), and a photoinitiator is overcoated withan oxygen/moisture barrier layer (e.g., a copolymer of an acrylic acidand copolymerizable ethylenically unsaturated compound). Such elementsare relatively oxygen insensitive (by reason of the barrier layer), andwith proper selection of the barrier layer can be developed with basicsolutions after exposure. These elements remain relatively slow andrequire the additional coating operation to provide the barrier layer.In addition to the time and cost factors resulting from the overcoatingoperation, careful control of solvents and conditions in this step mustbe observed to avoid sensitometric damage to the photosensitive layers.

Other radiation sensitive compositions known in the art include those ofU.S. Pat. No. 3,827,956. This ultraviolet radiation sensitivecomposition comprises (1) an acrylic monomer (e.g., pentaerythritoltriacrylate), (2) an acrylate oligomer (e.g., the reaction product oftoluene diisocyanate with two equivalents of 2-hydroxyethylmethacrylate), and (3) a halogenated polynuclear lactone catalyst. U.S.Pat. Nos. 3,297,745; 4,017,649; and 4,065,627 describe other acrylateend-capped urethane oligomers which can be homopolymerized orcopolymerized with other ethylenically unsaturated compounds. Thesematerials are photopolymerizable with relatively high radiationsensitivity and low oxygen sensitivity, but they are not base solubleand have no base developable printing plate capability because of this.These compositions also have poor bonding characteristics to metalsurfaces such as zinc and aluminum.

SUMMARY OF THE INVENTION

It has been found that high speed radiation sensitive photopolymerizablecompositions with excellent adhesion to certain substrates, especiallyaluminum surfaces, which compositions are suitable for use in radiationsensitive printing plates and color proofing sheets can be made. Thesecompositions also can have extensive shelf stability and oxygeninsensitivity, and the polymers produced therefrom are tough and have along service life. The compositions are also base soluble and can bedeveloped in basic solutions in printing plate processes.

The photosensitive compositions of the present invention comprise (1) anethylenically unsaturated free radical polymerizable end-cappedoligomer, the bridging oligomeric portion between the unsaturatedcapping groups having carboxyl group substitution thereon, (2) apolymeric binder, (3) at least one free radical polymerizable monomerhaving at least one ethylenically unsaturated group, and (4) a radiationsensitive initiator system capable of initiating free radicalpolymerization upon absorption of electromagnetic radiation.

A storage stable photosensitive imaging element of particular use inproviding base developable printing plates can be made by applying thephotosensitive compositions of the present invention to a support layer.

Particularly improved compositions comprising the photosensitiveoligomers, limited classes of binder, polymerizable monomers, andphotoinitiation systems have unexpectedly high radiation sensitivity andno oxygen or moisture sensitivity.

DETAILS OF THE INVENTION

There are basically four essential ingredients of the radiationsensitive compositions of the present invention, (1) an oligomer, (2) abinder, (3) a polymerizable monomer, and (4) a photoinitiation system.All four of these materials must be present in the polymerizablecomposition for it to work well in photoimagable recording elements asin lithographic printing processes. Generally, the compositions compriseper 100 parts total:

10 to 60 parts by weight of oligomer,

10 to 60 parts by weight of binder,

10 to 60 parts by weight of monomer, and

0.1 to 12.0 parts by weight of photoinitiator system.

It is preferred to have as the photoinitiator system a photosensitizerand a compound which when photosensitized is capable of initiating freeradical polymerization. In the practice of this invention the secondcompound is defined as an initiator. The photoinitiator system is morepreferably present in an amount of 0.5 to 10 parts. Preferably, thephotosensitive composition comprises per 100 parts total:

15 to 45 parts by weight of oligomer,

15 to 35 parts by weight of binder,

25 to 50 parts by weight of monomer,

0.2 to 10 parts by weight of initiator (more preferably 2 to 8), and

0.1 to 5 parts by weight of photosensitizer (more preferably 1 to 4).

Most preferably the compositions of the present invention comprise per100 parts total, by weight:

20 to 35 parts oligomer,

20 to 30 parts binder,

30 to 50 parts monomer,

2 to 6 parts initiator, and

1 to 3 parts photosensitizer.

Generally, the photosensitive compositions of the invention are preparedby mixing the components in a low boiling (at atmospheric pressureboiling at less than about 150° C.) polar solvent that is not reactivewith carboxyl groups or ethylenically unsaturated groups, such asmethanol, ethanol, propanol, acetone, methylethyl ketone,tetrahydrofurane or mixtures thereof. There may even be water presentalthough less than 50% by weight of water in the solvent is preferred.The amount of solvent used (generally 0 to 98% by weight, preferably 10to 96% by weight and in lithographic applications 85 to 95% by weightsolvent is most preferred) depends upon the desired viscosity anddesired coating thickness. It is often desirable to add a surfactant orcoating aid, but these aids, including the solvent are not functionallyrequired for practice of the invention, but are merely better modes ofpractice. 0.001 to 2% of surfactant, particularly silicone orfluorocarbon surfactants will usually be sufficient.

These compositions may contain any number of additional useful additivessuch as dyes, pigments, coating aids, surfactants, etc.

The coating weight of the compositions of the present invention isusually 0.3 to 9 g/m², preferably 0.5 to 5 g/m², and most preferably 0.8to 2.4 g/m². Suitable substrates include resin coated paper, varioustransparent or opaque plastic sheet or film, metal sheets and foils(preferably aluminum substrates that have been grained and anodized. Thecoated substrates must be maintained in the absence of light unless theelement is sensitized to a narrow range of the electromagnetic spectrumoutside the range of normal light and the element is provided with afilter layer which excludes normal visible light.

The preferred utility of the photopolymerizable compositions of thepresent invention is as a presensitized plate for use in printingoperations such as in the formation of lithographic plates. Thisstructure comprises a grained and anodized aluminum substrate coatedwith from 0.3 to 9 g/m² of the compositions of the present invention.Grained substrates are surfaces which have been textured or roughened.This treatment is well known in the art and can be effected by brushgraining (roughening with an abrasive material), chemical etching, orelectrochemical graining. Anodizing is the well known anodic oxidationof metal surfaces. Polymer top coat layers used in these constructionsmust be dissolvable in aqueous alkaline solutions of pH 8-13 such as theaqueous developers of the examples.

A generic structural formula for the urethane oligomers can be drawn asfollows: ##STR1## wherein E is an ethylenically unsaturated, freeradical polymerizable group, preferably selected from acryloyloxyalkoxy(alternatively named acryloxyalkoxy), methacryloylalkoxy (alternativelynamed methacryloxyalkoxy), vinylalkoxy, and allyloxy,

D is the residue of a polyisocyanate (preferably a diisocyanate) havingat least two of its --N═C═O groups reacted to form ##STR2## D bonding Eto R, A is a carboxylic acid containing group, (e.g., ##STR3## a is anumber having an average value between 2 and 20, b is a number having anaverage value between 0.3 and 10, and

m=1 to 6,

R is the residue of a polyol having at least a+b hydroxyl grops and anumber average molecular weight between 90 and 10,000, the residueformed by removal of hydrogen from the hydroxyl groups.

The backbone of the oligomer, group R, may be any aromatic or aliphaticpolyol having a molecular weight between 90 and 10,000. The backbone ofthe oligomer may be any oligomer with the requisite molecular weight andnumber of hydroxyl groups, but polyesterpolyols and polyoxyalkylenepolyols are preferred. Linear oligomeric polyols are useful but thebranched or three-dimensional polyols such as polycaprolactone polyolsare preferred. The backbone may be prepared by any of the many wellknown methods of forming polyhydroxyl substituted oligomers having amolecular weight between 90 and 10,000. The polyols must have a hydroxyequivalent weight of between 45 and 5,000 to be useful according to thepresent invention. Preferably the polyol has a hydroxy equivalent weightbetween 90 and 4,000 and most preferably between 200 and 2,000.

The oligomers backbone may be homopolymeric, copolymeric, graftpolymeric, or mixtures thereof. For example, polycaprolactone polyolsmay be used, or lower molecular weight polycaprolactone polyols (averagemolecular weights of less than, for example, 500) may be joined bypolyacids (preferably dicarboxylic acids) or by polyisocyanates(preferably diisocyanates) to form higher molecular weight oligomerbackbones.

In the synthesis of the oligomers useful in the present invention, it ispreferred to join the E-D substituent to the oligomeric backbone R byfirst separately forming an adduct of the polyisocyanate of which D is aresidue by reacting one mole of the diisocyanate with one mole of anethylenically unsaturated free radical polymericable monomer having onehydroxyl group. The adduct formed is then reacted with a hydroxyl groupon the oligomer polyol backbone (the reaction being with an isocyanategroup). In an alternative method where the compound with the freeradical polymerizable group with one hydroxyl group and thepolyisocyanate are added to the oligomeric polyhydroxy backbone beforeforming the E-D adduct, the polyisocyanate will act both as a polymerextender for the oligomer and as an adduct former with the free radicalcontaining compound. In such a reaction there would be far less controlover the final product and there would be a tendency for the oligomer togel. Therefore the free radical polymerizable monomer and thepolyisocyanate (preferably diisocyanate) in an independently runsynthesis form, for example, an isocyanatoalkylacrylate,isocyanatoalkylmethacrylate, an isocyanato alkyl ether, orisocyanatoalkylvinyl ether adduct.

The adduct (E-D) formed in that step is then caused to react with thepolyhydroxy containing backbone so that the remaining isocyanate groupof the adduct reacts with some, but not all, of the hydroxyl groups onthe oligomer to bond thereto.

The carboxylic acid groups are added to the oligomeric backbonepreferably after addition of the free radical polymerizable moieties byreaction of remaining hydroxyl groups on the oligomeric backbone with acompound having free carboxyl groups. Preferably such a compound is adicarboxylic acid or anhydride so that the linking bond to theoligomeric backbone is an ester group. An isocyanate linkage can beformed by first making an acid-isocyanate adduct.

A more specific formula representing preferred oligomeric materials isas follows: ##STR4## wherein D, a, and b are as defined above,

E is selected from ##STR5## and --(CH₂)_(n) O--CH₂ --CH═CH₂, where R⁴ is--H or --CH₃, and n is an integer of from 2 to 4 inclusive,

R¹ is the residue formed by the removal of active hydrogen atoms andhydroxyl groups from oligomeric Ω-hydroxy carboxylic acids or theresidue formed by the removal of active hydrogen atoms and hydroxylgroups from oligomeric diols,

R² is a residue, having a valence of a plus b, of an aliphatic polyolhaving the formula R⁵ (OH)_(a+b) after removal of a+b hydrogens fromhydroxyl groups, or a polyol having the formula ##STR6## after removalof a+b-1 hydrogens from hydroxyl groups wherein R⁵ is the residue of analiphatic polyol radical formed by having the OH groups removedtherefrom and having 3 to 10 valences substituted with OH groups andwhich can have one or two ether oxygen atoms in the aliphatic backbone,and

R³ is the residue of a dicarboxylic acid having both ##STR7## removedtherefrom.

Preferably the molecular weight of (R¹)_(a) R² (R^(i))_(b) is between200 and 5,000.

Particularly desirable aliphatic polyols from which R² is formed arepolyether polyols, polyester polyols, polylactone polyols, polyolefinpolyols, polydiene polyols, polysiloxane polyols, poly(alkylacrylate)polyols, and poly(glycidyl ether) polyols.

A particularly desirable material is represented by the structuralformula ##STR8## wherein R³ and R⁴ are as defined above,

c is 2 to 5 inclusive,

p is a number average value of 2 to 7.7,

q is a number average value of 0.3 to 4,

R⁶ is the residue of a diisocyanate having two --N═C═O groups removedtherefrom and preferably is an aromatic residue thereof, and

R⁷ is an organic triyl radical which is the residue of an organic polyolwith at least three hydroxyl groups removed therefrom and having amolecular weight of from 90 to 10,000, preferably selected fromaliphatic triols, tetrols and pentols, poly(oxyalkylene)triols, tetrolsand pentols, polyestertriols, tetrols and pentols, polylactonetriols,tetrols and pentols, polyolefintriols, tetrols and pentols,polyacrylatetriols, tetrols and pentols, polyalkylacrylatetriols,tetrols and pentols, and polysiloxanetriols, tetrols and pentols.

Another particularly desirable material can be represented by ##STR9##wherein R³ and R⁶ are as defined above,

d is 1 to 6 inclusive,

e is an average value of 0.5 to 5 inclusive,

f is an average value of 1 to 6 inclusive,

R⁸ is the divalent hydrocarbon radical which is the residue of anorganic polyisocyanate (preferably diisocyanate) with two isocyanategroups removed therefrom,

R⁹ is an alkanepolyyl radical having a valence of h+1 that is theresidue of an alkanepolyol having h+1 hydroxyl groups removed therefrom(preferably having h+1 hydroxyl groups before removal), saidalkanepolyol having a molecular weight of from 100 to 10,000 andpreferably 200 to 2,000, wherein h is an integer of from 2 to 8.

The general method of preparing the oligomers of the present inventionis as follows.

STEP ONE--Preparation of a one-to-one adduct of a hydroxyalkyl (freeradical polymerizable) material and a polyisocyanate, preferably adiisocyanate. This is done by reacting the two materials in a one-to-oneratio.

STEP TWO--Reaction of an organic polyol having X number of hydroxylgroups with up to X-1 moles of the adduct of STEP ONE. This forms aurethane oligomer having both ethylenically unsubstituted groups and atleast one free hydroxyl group. Although, of course, in this reactionsome individual oligomeric moieties may have all X hydroxyl groupsreacted with the isocyanate, by control of the proportions of isocyanateadduct and polyol, the number average of free hydroxyl groups on theurethane oligomer will be at least one.

STEP THREE--The free hydroxyl groups on the product of STEP TWO areesterified with a polycarboxylic acid (preferably a dicarboxylic acidand most preferably an anhydride of a diacid). This reaction forms thecarboxyl-substituted, ethylenically unsaturated urethane oligomer of theinvention.

The adduct of the hydroxyalkylacrylate and the diisocyanate of STEP ONEhas the general formula: ##STR10## wherein R⁶, R⁴ and a are as definedabove, and

R⁶ is preferably tolyl, and

R¹⁰ is an aliphatic group and preferably is (CH₂)₂₋₆.

It is preferred to use diisocyanates such as tolylene-2,4-diisocyanateand isophorone diisocyanate because of the great differential betweenreactivities of the isocyanate groups thereon. Without thisdifferential, the product would have to be purified or else there wouldbe less control over the subsequent product.

Such adducts are prepared by the addition of about 0.9 to 1.1 molarequivalent of the hydroxyalkylacrylate to one mole of organicdiisocyanate while stirring the reaction mixture. Generally, it isdesirable to hold the temperature below about 30° C. during theaddition. The reaction can be complete after stirring the mixture for 10minutes to an hour or more. If not completed that quickly, the reactionmay be completed by further heating the mixture at temperatures of 50°or more for at least an hour. Since many of the reaction products areviscous liquids or solids (the reaction product of 2-hydroxyethylmethacrylate and 2,4-toluene-diisocyanate is a solid) it is preferableto add 0.25 to about 35 parts by weight of a non-functional groupcontaining solvent, such as methylethyl ketone, acetone,tetrahydrofurane or the like. The solvent can be added at the beginningof the reaction, or along with the addition of the hydroxyalkylacrylate.Although not always necessary, it is often desirable to add a catalystto effect the reaction between the hydroxyl group of thehydroxyalkylacrylate and one of the isocyanate groups of the organicdiisocyanate. Suitable catalysts for the reaction are well known; anexample of which is dibutyltin dilaurate.

STEP TWO is accomplished by adding over a period of one to five or morehours either the product of STEP ONE to an organic polyol as definedabove while heating the mixture at about 50° to 100° or vice-versa. Asfor STEP ONE, a catalyst such as dibutyltin dilaurate can be used tofacilitate the reaction. It is often desirable to add a polymerizationinhibitor such as 2,6-di(t-butyl)-4-methylphenol to prevent prematurepolymerization. The ratio of diisocyanate-hydroxyalkylacrylate adduct toorganic polyol is chosen so that one mole of oligomer obtained by thereaction contains at least two acrylic groups but leaves at least 0.3equivalents unreacted hydroxyl groups.

STEP THREE is carried out, generally without isolating the product ofSTEP TWO, by esterification of unreacted hydroxyls in the product ofSTEP TWO with an anhydride of a dicarboxylic acid. Preferably, theesterification is accomplished by adding an amount of an anhydride of adicarboxylic acid such as preferably succinic acid anhydride or adipicacid anhydride and continuing heating 50° to 100° C. for 3 to about 10hours, the higher the temperature, the shorter the heating timerequired. Depending on the extent of carboxylation desired, there isused from about 0.3 to about 4 moles of anhydride per mole of organicpolyol originally present in the reaction mixture. The esterification,however, can be preformed using in place of the anhydride an ester ofthe dicarboxylic acid, viz., the methyl or ethyl ester and by esterinterchange distill of the corresponding methanol or ethanol formed.Esterification can also be preformed using other reactive derivatives ofthe dicarboxylic acid such as the diacid chloride and removing thehydrogen chloride formed. Sometimes it is necessary to add a basiccatalyst, such as lithium acetate, to increase the rate of thisreaction.

Controlling the ratio of the number of acid (carboxylic acid) groups onthe oligomer to the gram molecular weight of t-e oligomer is aneffective way of controlling the bondability of the composition to asubstrate after photoinitiated reaction. With increasing acidconcentration, the composition is removed more easily in development. Awide range of ratios can be used, depending upon the performancecharacteristics desired in the final product. A composition having aratio of molecular weight to acid groups between 67 and 17,000 isuseful. It is preferred to have the ratio of molecular weight to acidgroups in the oligomer between 500 and 5,000, and most preferablybetween 800 and 3,000.

Binders

The second of the critical elements in the photopolymerizablecompositions of the present invention is the binder. This material is anorganic film forming polymer having a molecular weight of at least6,000, preferably 12,000 and most preferably at least 15,000. It isdesirable, but not essential for practice of the present invention, forthe binder to have a labile hydrogen or easily abstractable hydrogenthereon. The polymer preferably has a molecular weight of no greaterthan 100,000, preferably no greater than 80,000 and most preferably nogreater than 50,000, although binders with molecular weights up to2,000,000 or 3,000,000 are known in the art. To be a labile or easilyabstractable hydrogen, a hydrogen in the binder must be attached to acarbon atom having an adjacent heteroatom selected from N, S, Se, and O.Preferably the heteroatom is N, S, or O. It is also preferred that thecarbon having the easily abstractable hydrogen thereon is in a 5, 6, or7-membered heterocyclic ring comprised of C, N, S, and O atoms, withpreferably two heteroatoms adjacent to the carbon atom having the labilehydrogen. The carbon atom bearing the labile hydrogen can be primary,but is preferably secondary or tertiary. The greater the ease ofabstractability the lower the proportion of binder that the compositionneeds, although not necessarily in a linear relationship. Preferredbinders are the polyvinyl acetals such as polyvinyl formal, polyvinylbutyral, and mixtures thereof. Poly(vinyl methylether, polyvinylalcohol, hydroxyalkylcellulose (e.g., hydroxypropylcellulose),polyamides, polyvinylacetate, polyvinylacetate-polyvinylchloridecopolymers, polyethyleneoxides, and polyacrylates (e.g.,polyalkylmethacrylates have also been found to work well).

The rate or quantum efficiency of double bond conversion (i.e.,polymerization) and the photosensitivity of various coatings exposed inair are a function of the type of polymeric binder used. While somepolymers give no increase in rate and photosensitivity to thecomposition, many polymers have been found that give surprisingly largeincreases. Amongst the polymers that have been shown to give an increasein the rate of conversion of double bonds include polyvinylacetals,polyvinylalcohol, hydroxyalkylcellulose (e.g., hydroxypropylcellulose),polyamides, polyvinylacetate, polyvinylacetatevinylchloride,polyethyleneoxide, and polyalkylmethacrylates. Polymers that do not givean increase include certain aliphatic hydrocarbon resins, celluloseacetatebutyrate, certain polyurethanes such as Estane®, and linearsaturated polyesters.

It should be understood by those knowledgeable in the art that not allpolymers that give a rate increase are necessarily the best binders forlithographic plate coatings although they are still useful and desirablein other imaging processes such as duplicating film and proofingsystems. Other properties such as solubility, water sensitivity andadhesion must be considered in choosing a polymeric binder forlithograhic plates.

The exact function of the binder in the compositions of the presentinvention is not understood. The labile hydrogen thereon is believed tobe desirable, as many materials without a labile hydrogen do not appearto work as well as those with labile hydrogens, although some do in factwork well. Oxygen barrier characteristics may be additionally desirablein the binder polymer but such characteristics are not known to beessential.

Monomers

Another of the critical materials in the photopolymerizable compositionsof the present invention is the monomer. This material is a free radicalpolymerizable monomer having one or more ethylenically unsaturatedgroups, and preferably 2 to 4 ethylenically unsaturated groups such asacrylate, methacrylate, vinyl and allyl. Preferred are compounds havingmultiple acrylate and methacrylate groups, e.g., acrylic esters of lowmolecular weight polyols, such as trimethylolpropanetriacrylate,pentaerythritol tetraacrylate and triacrylate, etc. Preferably thesemonomers have a molecular weight of less than 2,000 and more preferablyless than 1,000.

Suitable free radical polymerizable monomers useful in the compositionsof the invention are well known and listed in many patents, e.g., U.S.Pat. Nos. 3,895,949 and 4,037,021. Preferred monomers are thepolyacrylate and polymethacrylate esters of alkanepolyols, e.g.,pentaerythritol tetraacrylate, tris(2-acryloxyethyl)isocyanurate,tris(2-methyacryloxyethyl)isocyanurate, 2-acetoxyethyl methacrylate,tetrahydrofurfurylmethacrylate, 1-aza-5-acryloxymethyl-3,7-dioxabicyclo[3.0.0] octane (ADOZ) bis[4-(2-acryloxyethyl)phenyl]dimethyl methane,diacetone acrylamide, and acrylamidoethyl methacrylate.

Initiator

The compositions of the present invention must also have a radiationsensitive system capable of initiating free radical polymerization uponabsorption of radiation. Free radical initiators are materials known inthe art, such as Free-Radical Chemistry, D. C. Nonhebel and J. C.Walton, University Press (1974). Particularly suitable free radicalgenerators can be selected from many classes of organic compoundsincluding, for example, organic peroxides, azo compounds, aromaticdiazonium salts, aromatic iodonium salts, aromatic sulfonium salts,aromatic phosphonium salts, quinones, benzophenones, nitroso compounds,acyl halides, aryl halides, hydrazones, mercapto compounds, pyryliumcompounds, triarylimidazoles, biimidazoles, chloroalkyltriazines, etc.These materials, in generaly, must have photosensitizers therewith toform a photoinitiator system. Photosensitizers are well known in theart.

Additional reference in the art to free radical photoinitiator systemsfor ethylenically unsaturated compounds are included in U.S. Pat. No.3,887,450 (e.g., column 4), U.S. Pat. No. 3,895,949 (e.g., column 7),and U.S. Pat. No. 4,043,819. Preferred initiators are the onium salts asdisclosed in U.S. Pat. Nos. 3,729,313; 4,058,400; and 4,058,401. Otherdesirable initiators are biimidazoles (disclosed in U.S. patentapplication Ser. No. 824,733, filed Aug. 15, 1977) andchloroalkyltriazines as disclosed in U.S. Pat. No. 3,775,113. Thesereferences also disclose sensitizers therein. Another good reference tophotoinitiator systems is Light-Sensitive Systems, J. Kosar, 1965, J.Wiley and Sons, Inc., especially Chapter 5.

PREPARATION I

A polycaprolactone hexol is prepared for use in forming a carboxylsubstituted urethane oligomer.

63.5 grams dipentaerythritol, 228 grams epsilon-caprolactone, and 0.02grams 2,6-di-t-butyl-4-methyl phenol (as an oxidation inhibitor) wereadded to a 500 ml, three-neck flask which had been fitted with anoverhead mechanical stirrer and a condenser. The liquid was deoxygenatedfor 20 minutes by bubbling with dry nitrogen from a gas dispersion tube.This tube was then replaced with a gas inlet adapter and the reactionmixture was heated while maintaining a slight positive pressure withnitrogen. The mixture was maintained at 170° C. for 5 hours undercontinual stirring. The reaction mixture was then allowed to cool toroom temperature under a nitrogen atmosphere. This material is referredto as P-I. This procedure is similar to that in U.S. Pat. No. 3,169,945.

PREPARATION II

A urethane oligomer (hereinafter P-II) was prepared according to thefollowing procedures.

A 1000 ml three-neck flash was fitted with an adapter, mechanicalstirrer, thermometer, addition funnel, and drying tube. To this flaskwas charged 175 grams of polycaprolactone hexol P-I and 60 ml ofmethylethyl ketone. A solution of 13 grams of 2,4-tolylene diisocyanatein 9 ml of methylethyl ketone was slowly dripped into the first solutionwith stirring at room temperature. The addition was completed in 20minutes and the reaction mixture stirred for 90 minutes at 30° C., afterwhich time infrared spectroscopy showed that essentially all theisocyanate had reacted.

To a second flask fitted with an overhead mechanical stirrer,thermometer, addition funnel, and drying tube was charged 86.1 grams of2,4-tolylene diisocyanate. To the addition funnel was added 70.2 grams2-hydroxyethylmethacrylate (hereafter HEMA) and 0.02 grams of theinhibitor of the previous preparation, which was then slowly added withstirring to the diisocyanate while maintained below or at 30° C. Theaddition was completed in 15 minutes and after 40 minutes of reactiontime, a white solid formed. The solid was dissolved in 45 ml ofmethylethyl ketone by heating to 45° C. and held at that temperature for10 minutes to complete the reaction.

The flask containing the reaction product (adduct) of thepolycaprolactone hexol (P-I) and the 2,4-tolylene diisocyanate washeated to 67° C. and the solution of the HEMA/2,4-tolylene diisocyanateadduct in methylethyl ketone was added slowly with stirring over aperiod of 2 hours. 27 grams of succinic anhydride was then added with anadditional 0.02 grams of the inhibitor. Heating and stirring wascontinued until the anhydride had completely reacted (about 5-6 hours).

The final product is a carboxyl substituted urethane oligomer, P-II.

PREPARATION III

The preparation of a second carboxyl substituted urethane oligomer ishere described.

To a 500 ml three-neck flask was charged 29.2 grams of a poly(propyleneoxide)triol having a molecular weight of 740, 25 ml ethyl acetate, and0.007 grams of methylhydroquinone as a reaction inhibitor. The flask washeated in a 65° C. oil bath with stirring and 13.0 grams HEMA and 17.4grams tolylene diisocyanate were added simultaneously from additionfunnels. After addition of one half of these reactants, the reactionmixture was stirred for another 30 minutes. Then 0.001 grams SnCl₂catalyst and 0.004 grams 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate were added. The reaction mixture was stirred another 30minutes and then the remainder of the HEMA and diisocyanate were addedslowly. Stirring was continued overnight. Infrared analysis showed nofree isocyanate groups after that time. To this reaction mixture wasadded, with stirring, 1.4 grams succinic anhydride. The temperature wasraised to 93° C. and held there until the anhydride was completelyreacted. The mixture was then cooled and diluted to 50% weight solutionof P-III oligomer in ethyl acetate.

PREPARATION IV

A 250 ml flask was charged with 21.2 grams of a polycaprolactone polyolhaving a molecular weight of about 540, 25.1 ml of ethyl acetate and0.007 grams methylhydroquinone as an antioxidant. 17.4 grams oftolylene-2,4-diisocyanate and 13.0 grams of 2-hydroxyethylmethacrylate(HEMA) were individually added to addition funnels on the flask. Thepolyol solution was heated to 67° C. and the diisocyanate and HEMA wereadded dropwise with rapid stirring until half of each material wasadded. At this point stirring and heating were continued for 30 minutes.0.002 grams SnCl₂ and 0.008 grams of3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate were addedand the solution stirred for another 30 minutes. The remainder of thediisocyanate and HEMA was added dropwise and then an additional 5 ml ofethyl acetate was added. The mixture was stirred at 67° C. overnight.When isocyanate was no longer detectable by infrared analysis, 1.4 gramsof succinic anhydride was added along with 10 ml of ethyl acetate. Thetemperature was raised to 100° C. and the reaction of the anhydride wasindicated by infrared analysis as essentially complete after five hours.

This resulting material, a carboxylic substituted urethane oligomer, isreferred to as P-IV and is useful in the practice of the presentinvention.

PREPARATION V

A particularly useful binder material for the oligomers was prepared asfollows. A low molecular weight polyvinyl alcohol (88% hydrolyzedpolyvinylacetate) was reacted with butyraldehyde and acrolein using anacid catalyst, preferably sulfuric acid. The proportion of reactants was100/43.2/6.4 respectively. The product was precipitated from water witha dilute weak basic solution (NaHCO₃). Analysis of the product showedthe empirical formula to be close to that based on the stoichiometry ofthe reaction, ##STR11## This material is hereinafter referred to as P-V.

PREPARATIONS VI-XI

Six additional oligomers were prepared for evaluation in the presentinvention.

P-VI was prepared by first placing 128.8 g of 2,4-toluenediisocyanateinto a three neck, 250 ml flask equipped with a mechanical stirrer and apressure equalizing dropping funnel. The flask was maintained at roomtemperature with a water bath. Hydroxyethylmethacrylate (106.6 g) and0.089 butylated hydroxy toluene and 100 g methylethyl ketone were addedslowly over a 30 minute period. The reaction was stirred for one hour atroom temperature. Methylethyl ketone was added and the reaction mixturewas heated to 45° C. for 3 hours to complete the reaction.

P-I (350 g of 79% solids in methylethyl ketone) was placed into a 500ml, three neck flask equipped with a mechanical stirrer, pressureequalizing dropping funnel and 26.0 g 2,4-toluenediisocyanate was addedover a 30 minute period. The temperature rose to 32° C. The mixture wascooled to room temperature and stirred over the weekend. The firstreaction product from the above synthesis was added over a four hourperiod to this second solution which had been heated to 65° C. Heatingwas continued for ten hours to form the second reaction product.

1.8 g of succinic anhydride and 0.1 g lithium acetate were added to112.4 g (71% solids in methylethyl ketone) of the second reactionproduct and the entire mixture heated to 78° C. for twelve hours tocomplete the reaction and form oligomer P-VI.

P-VII was prepared by placing 112.4 g (71% solids in methylethyl ketone)of the second reaction product in the preparation of P-VI into a 500 mlthree neck flask with stirrer and condenser and then adding 2.4 gsuccinic anhydride and 0.1 g lithium acetate. The mixture was heated to78° C. for 12 hours until the reaction was complete to form P-VII.

P-VIII was formed by placing 112.4 g (71% solids in methylethyl ketone)of the second reaction product in the preparation of P-VI into a 500 mlthree neck flask with stirrer and condenser with 5.5 g siccinicanhydride and 0.1 g lithium acetate. The reaction mixture was thenheated to 78° C. for 32 hours until the reaction was complete to formP-VIII.

P-IX was formed by first preparing a polycaprolactone hexol byintroducing 342 g caprolactone and 127 g dipentaerythritol into a 1000ml reaction kettle equipped with a thermometer, mechanical stirrer andcondenser. The reaction mixture was deoxygenated by bubblinb drynitrogen through a gas dispersion tube for about 30 minutes. The gasdispersion tube was then replaced with a gas inlet adapter and thereaction was maintained under a slight positive nitrogen pressure. Thereaction mixture was heated in an oil bath at 165°-170° C. withcontinuous stirring for 24 hours. The product was allowed to cool toroom temperature while under a nitrogen atmosphere.

141.0 g of the polycaprolactone hexol and 50 g of methylethyl ketonewere placed in a 1000 ml flask equipped with a pressure equalizingdropping funnel and a mechanical stirrer. This solution was maintainedat room temperature by using a water bath while 2,4-toluene diisocyanate(13.0 g) in 20 g of methylethyl ketone was added over a 25 minute periodthrough the dropping funnel with continuous stirring. Stirring at roomtemperature was continued for 22 hours to form the second reactionproduct.

38.2 g of 2,4-toluene diisocyanate and 0.2 butylated hydroxytoluene wereintroduced into a 250 ml three neck flask equipped with mechanicalstirrer, pressure equalizing dropping funnel and thermometer.Hydroxymethyl methacrylate (31.2 g) was added with continuous stirringover fifteen minutes at a temperature below 30° C. The mixture wasstirred for one hour and a white solid formed. 20 ml of methylethylketone was added and the mixture heated to 45° C. for three hours tocomplete formation of the third reaction product.

69.7 g of the second reaction product and 0.02 g butylated hydroxytoluene were added to a 500 ml three neck flask with a mechanicalstirrer, condenser, and pressure equalizing dropping funnel. Thissolution was heated to 69° C. with continuous stirring. The entireportion of the third reaction product was added to this solution overone hour. Heating and stirring were continued for thirteen hours to formthe fourth reaction product.

13.0 g of succinic anhydride and 0.4 g of lithium acetate were added tothe fourth reaction product and the solution heated at 70° C. to 80° C.with continuous stirring to form P-IX.

P-X was prepared by first forming a polyol by placing 93.1 gtripentaerythritol and 303.2 g caprolactone in a 1 liter reaction kettleequipped with mechanical stirrer, condenser, and thermometer. Thereaction mixture was purged with dry nitrogen for 30 minutes, and a gasinlet tube affixed thereto. Positive nitrogen pressure was maintainedover the reaction mixture as it was heated to 165°-170° C. for 91/2hours, then allowed to cool to room temperature.

300 g of this polyol and 75 g of methylethyl ketone were introduced intoa 1000 ml flask equipped with stirrer, dropping funnel and thermometer,16.4 g of 2,4-toluene diisocyanate was added through the dropping funnelover 10 minutes. The temperature of the mixture rose to between 28°-32°C. and continued for about 31/2 hours to form the first reactionproduct. 153 g of this product (as 80% solids in methylethyl ketone) wasadded with 0.04 g butylated hydroxytoluene into a flask and heated to65°-70° C. Over a period of 2 hours the third reaction product ofpreparation IX was added to this solution and heated for an additionalthree hours.

18.5 g of succinic anhydride and 0.5 g of lithium acetate was added tothe above resulting solution and the mixture heated at 70°-80° C. for 22hours to product P-X.

P-XI was prepared by first forming an adduct of 2,4-toluene diisocyanate(26.8 g) and hydroxyethylmethacrylate (22 g) in 30 ml of methylethylketone with 0.02 g butylated hydroxytoluene in the same procedure usedin forming the third reaction product of preparation IX. This productwas added over a one hour period to the product of the second solutionof P-VI (87.7 g as 80% solids in methylethyl ketone) and 0.02 gbutylated hydroxytoluene and heated to 65°-70° C. Heating was continuedfor 71/2 hours at about 67° C.

19.6 g of succinic anhydride and 0.4 g lithium acetate were then addedto the solution and heated at 75° C. for 84 hours to form P-XI.

Preparation XII

A urethane oligomer (hereinafter P-XII) was prepared according to thefollowing procedure.

A 1000 ml three neck flask with adapter fitted with an overheadmechanical stirrer, thermometer, addition funnel and drying tube wascharged with 180 g of a polypropylene oxide polyol of molecular weight600 and 90 ml of methylethyl ketone. A solution of 34.8 g 2,4-toluenediisocyanate in 30 g of methylethyl ketone was added with stirring atroom temperature. The addition was completed after 80 minutes andstirring was continued at room temperature for 90 minutes. After theaddition of 0.02 g 2,6-di-t-butyl-4-methyl phenol, the temperature wasincreased to 45°-55° C. for about 15 hours at which time isocyanategroups were no longer detected by infrared analysis.

To a 250 ml one neck flask with a magnetic stirrer and drying tube wascharged 95.7 g 2,4-toluene diisocyanate. 78 g of2-hydroxyethylmethacrylate was added over a period of about 10 minuteswhile maintaining the temperature at less than 30° C. with a cold waterbath. After about 40 minutes of total reaction time a white solid formedand 45 ml of methylethyl ketone was added. The solution solidified onstanding overnight and was redissolved by warming to about 45° C.

The product from the reaction of polyol and 2,4-toluene diisocyanate washeated to 67° C. and the product from the 2-hydroxyethylmethacrylate and2,4-toluene diisocyanate was added over a period of about 30 minutes.After 6 hours 27 g of succinic anhydride and 1.05 g of lithium acetatewere added. After about 28 hours of heating at 53° C. to 70° C. theanhydride was determined to be completely reacted by infrared analysis.

EXAMPLES 1-4

A solution was prepared (in parts by weight) from 3.32 partspentaerythritol tetraacrylate, 1.87 parts P-II, 0.17 partstriethylamine, 0.34 parts of diphenyliodonium hexafluorophosphate, 0.17parts 4,4'-bis(dimethylamino)benzophenone (a photosensitizer for theiodonium catalyst) and 91.62 parts of n-propanol/water azeotrope (71.8%n-propanol and 28.2% water). Aliquots of this solution were prepared and2.50 parts by weight of different organic polymeric binders were addedto the solution.

Aluminum sheets which had been grained and anodized were coated withthese solutions using a #14 wire wound rod and then dried with a heatgun. The coated aluminum was then exposed for 13 seconds in a vacuumframe to a carbon arc having about a 5000 watt output and at about 1meter distance through a 21 step sensitivity guide and a neutral density0.51 filter. Exposed plates were developed by wiping with a weak basicaqueous solution of 0.63% sodium metasilicate and 0.23% sodium (loweralkyl) naphthalene sulfonate.

The binders used in the examples were:

1. P-V,

2. Poly(vinyl methyl ether),

3. Poly(vinyl formal), prepared from a polyvinyl acetate startingmaterial and having 85% of the acetate groups replaced by alcohol andformal groups (the polyvinyl acetate having a viscosity of about 12 cpat 25° C. as 86 grams in 1000 ml of benzene), and

4. Poly(vinyl butyral).

The following table shows the polymer retained after exposure to acertain number of steps and development by the weak basic solution.

    ______________________________________                                                       Steps                                                          Example          Solid       Ghost                                            ______________________________________                                        1                8           10                                               2                4           6                                                3                4           5                                                4                2           4                                                ______________________________________                                    

The "ghost" values indicate the lowest exposure from which photopolymerwas retained on the plate. The "solid" values indicate the exposurelevel at which the developed image density can no longer bedifferentiated from the background and is believed to be cured to thedesired level.

The numbers of the steps consecutively indicate an increase of about 40%in filtering strength. The higher the step number remaining afterdevelopment, the correspondingly higher sensitivity of the compositionexposed and developed.

EXAMPLE 5

The usefulness of the compositions of the present invention inconventional newspaper printing operations was evaluated here.

A solution was prepared having 17.2 grams pentaerythritol tetraacrylate,13.5 grams P-II (70% by weight in methylethyl ketone), 171.6 grams ofpolyvinyl formal in a 6% by weight solution in the azeotrope, 295 gramsof the n-propanol/water azeotrope, 4.3 grams of 20% triethylamine, 3.7grams of red pigment (Pigment Red 48, CI15865 in the Color Index) in acomposition of 1:2 weight ratio to polyvinyl formal (as describedabove), 1.74 grams diphenyliodonium hexafluorophosphate and 0.65 grams4,4'-bis(dimethylamino)benzophenone photosensitizer. This compositionwas coated on grained anodized aluminum using a squeeze roll coaterfitted with a rubber gravure sleeve. The coating weight was about 1.72grams/m². The coating was exposed in a vacuum frame by a carbon arc for40 seconds through a neutral density 0.5 filter and a newspapernegative. The coating was developed with the aqueous developing solutionof Examples 1-4 and then gummed with a standard substractive plate gum.The resulting printing plate was mounted on a high speed web press usingdirect lithographic techniques and produced 95,000 newspaper impressionswithout degradation of the image line copy or half-tones.

EXAMPLE 6

A solution was prepared from 7.72 grams of P-V, 327.4 grams of then-propanol/water azeotrope, 12.8 grams of pentaerythritol tetraacrylate,10.3 grams of a 69% by weight solution of P-II in the azeotrope, 3.2grams of a 20% solution of triethylamine in the azeotrope, 15.7 grams ofPigment Red 48 dispersed in P-V and the azeotrope (4:8:88), 1.3 grams ofdiphenyliodonium hexafluorophosphate and 0.65 grams of the benzophenonesensitizer of the previous examples. This solution was coated ontograined anodized aluminum using a squeeze roll coater fitted with arubber gravure sleeve at a coating weight of about 1.72 grams/m². Thecoatings were exposed from a pasteup with a laser imaging system, usingprimarily the 351 and 364 nm lines of an argon ion laser, (at 4milliJoules/cm²) exposure) and developed with the mild basic aqueousdeveloping solution of the previous examples, and gummed with acommercial substractive plate gum. The printing plates were mounted on aweb offset press and produced high quality impressions.

EXAMPLE 7

A solution was prepared from 12.8 grams of polyvinyl formal from a 6% byweight solution in the n-propanol/water azeotrope, 1.28 grams ofpentaerythritol tetraacrylate, 1.42 grams of P-III as a 50% by weightsolution in ethyl acetate, 24 grams of the azeotropic solution, 0.28grams of Pigment Red 48 in polyvinyl formal (1:2 weight ratio), 8 dropsof a 20% solution of triethylamine in the azeotrope, 0.13 grams ofdiphenyliodonium hexafluorophosphate and 0.065 grams of the benzophenonesensitizer of the previous examples.

This solution was coated onto grained anodized aluminum using a #14 wirewound rod. After exposure (from a 5000 watt output carbon arc for 13second through neutral density 0.51 filter) and development with theweak basic solution of the previous examples, a solid image at step 6was obtained, and a ghost image at step 7 was obtained.

EXAMPLE 8

A solution was prepared from 1.54 grams of P-V, 2.56 grams ofpentaerythritol tetraacrylate, 2.06 grams of P-II as a 70% by weightsolution in methylethyl ketone, 0.64 grams of triethylamine as a 20% byweight solution in the azeotrope, 4.7 grams of a dispersion of PigmentRed 48 in P-V and the azeotrope (4:8:88), 65.6 grams of the azeotrope,0.25 grams of diphenyliodonium hexafluorophosphate, and 0.13 grams of4,4'-bis(dimethylamino)benzophenone. This solution was coated with a #14wire wound rod onto a substrate comprising polyethylene film with a topcoat of TiO₂ and CaCO₃ in a polyurethane binder. This coating was airdried with a heat gun and overcoated with a 10% solution of lowmolecular weight (88% hydrolyzed polyvinyl acetate) poly(vinyl alcohol)with a small amount of inert surfactant as a coating aid. A #10 wirewound rod was used to coat this solution. The dried coating was exposedin a vacuum frame to a carbon arc for 13 seconds through a 0.5 neutraldensity filter, a half-tone negative, and a sensitivity guide. Theexposed coating was developed with an aqueous solution of 0.63% sodiummetasilicate and 0.23% sodium (lower alkyl)naphthalene sulfonate. Astrong magenta image on a white background was obtained. Solid 3 andghost 5 steps were visible and sharp 3-97% dots of at least a 110 linescreen were obtained.

EXAMPLES 9-15

The following examples show the necessity and interaction of thedifferent components of the system of the present invention. The effectof poly(vinyl alcohol) topcoats, normally used in the art as an oxygenbarrier, was also investigated.

Solutions were prepared with different combinations of representativeadditives. P-V was used as the binder, P-II as the carboxyl containingfree radical polymerizable oligomer, pentaerythritol tetraacrylate asthe free radical polymerizable monomer, diphenyliodoniumhexafluorophosphate (as 0.04 parts by weight) as the free radicalinitiator, ##STR12## as CEBH (0.01 parts by weight) as sensitizer, andpoly(vinyl alcohol) as a topcoat. The solutions having the compositionsnoted below in the table were coated on grained and anodized aluminum togive dry coating weights of from 1.06 to 1.61 grams/m². Where a topcoatwas present, the poly(vinyl alcohol) was applied at about the samecoating weight as the base coat. In the examples the solutions were madefrom isopropanol or methanol-methylethyl ketone-water solvents.Triethylamine was added in all examples in amounts equivalent to theacid in P-II.

The dried samples were exposed through a 21 step sensitivity guide for 2seconds with a 16,000 foot candle tungsten source. The exposed sampleswere developed by wiping with an aqueous solution of 0.35% sodiummetasilicate and 0.25% sodium (lower alkyl)naphthalene sulfonate.

    ______________________________________                                        Example No.                                                                            P-V     P-II    Monomer  Top Coat                                                                             Steps                                ______________________________________                                         9       0.3     0.0     0.4      No     1                                    10       0.3     0.4     0.0      No     1                                    11       0.0     0.5     0.4      No     0                                    12       0.0     0.5     0.4      Yes    10                                   13       0.3     0.2     0.4      No     9                                    14       0.3     0.4     0.2      No     10-11                                15       0.3     0.4     0.2      Yes    14                                   ______________________________________                                    

As can be seen from these results, the absence of any one of the threeingredients (binder, oligomer, or monomer) produces poor or uselessphotopolymerizable compositions. When a top coat is put on thecomposition without the binder (Example 12), the oxygen sensitivity ofthe system is reduced and it polymerizes well. Surprisingly, systemshaving the three components of the present invention work as well as thetop coated system (Examples 13 and 14), and when the systems of thepresent invention are combined with a top coat, even further improvedresults are obtained (Example 15). These results are surprising andhighly desirable.

EXAMPLE 16

A solution was prepared from 4 parts poly(m-diallylphthalate), 2 partsP-II, 4 parts pentaerythritol tetraacrylate, 5 parts methanol, 0.4 partsdiphenyliodonium hexafluorophosphate, 0.1 part CEBH, 0.4 parts ofPhthalocyanine Blue GS, and methylethyl ketone in 100 parts. This wascoated onto grained and anodized aluminum to give a dry coating weightof about 1.34 grams/m². This was overcoated with poly(vinyl alcohol) atabout the same coating weight as the base coat. The coating was airdried, then exposed and developed as in Examples 9-15.

The photopolymer was retained through step 12.

EXAMPLE 17

The same procedure as in Example 16 was used except that 4 parts oftris-methacryloxyethyl isocyanurate was substituted for thepentaerythritol tetraacrylate. The photopolymer was again retainedthrough step 12.

EXAMPLES 18-21

A solution was prepared from 0.3 grams P-V, 0.4 grams pentaerythritoltetraacrylate, 0.22 grams P-II, 0.04 grams diphenyliodoniumhexafluorophosphate, 0.02 grams of CEBH, 1.28 grams methylethyl ketone,0.47 grams water, 7.36 grams isopropanol, and 6 drops of a 20% by weightsolution of triethylamine in n-propanol. The solution was coated withwire wound rods onto grained and anodized aluminum at coating weights of0.95, 1.36 and 2.04 grams/m². Some of the coatings were overcoated witha 10% by weight solution of poly(vinyl alcohol) using a #8 wire woundrod. The coatings were exposed using an argon laser at 488 nm anddeveloped by wiping with a pad and an aqueous solution of a 0.35% sodiummetasilicate and 0.25% sodium (lower alkyl)naphthalene sulfonate. Thelaser beam was passed through a 21 step sensitivity guide. The exposurevalues (in milliJoules/cm²) listed are the exposures needed to give asolid step 6 for the various coating weights.

    ______________________________________                                         Example  Coating Weight g/m.sup.2                                                                      Top Coat Exposure                                   ______________________________________                                        18         .95            Yes      1.8                                        19        1.36            Yes      1.8                                        20        1.36            No       10-14                                      21        2.04            No       10                                         ______________________________________                                    

As can be seen, the top coat improves the compositions, but the uncoatedmaterials are still of excellent speed and quality even when exposed inthe presence of air.

EXAMPLES 22-32

Solutions were prepared as in Example 16 except that differentphotoinitiation systems were evaluated. Exposure was to a mercury vaporlamp having an output of 500 watts/inch at a distance of about 34 cmthrough an interference filter having a maximum transmission at 366 nmand a 21 step sensitivity guide. The table indicates the relativesensitivity of the system for the minimum exposure required to giveretained photopolymer with development as in Example 16.

    ______________________________________                                                                 Approx.                                                                       Absorption Relative                                  Ex.   Photoinitiation System                                                                           at 366 nm  Exposure                                  ______________________________________                                        22    4,4'-bis(dimethylamino)benzo-                                                                    0.3        0.26                                            phenone                                                                       2-o-chlorophenyl-4,5-di(m-                                                    methoxyphenyl)imidazole                                                       dimer                                                                         2-o-chlorophenyl-4,5-di-                                                      phenylimidazole dimer                                                         2-mercaptobenzoxazole                                                   23    Same as Example 22 0.01       0.88                                      24    4,4'-bis(dimethylamino)benzo-                                                                    0.1        2.2                                             phenone                                                                       diphenyliodonium hexafluoro-                                                  phosphate                                                               25    tetraphenyl benzidine                                                                            0.2        3.3                                             diphenyliodonium hexafluoro-                                                  phosphate                                                               26    tetraphenyl benzidine                                                                            0.1        4.8                                             diphenyliodonium hexafluoro-                                                  phosphate                                                               27    tetraphenyl benzidine                                                                            0.02       13                                              diphenyliodonium hexafluoro-                                                  phosphate                                                               28    2,4-bis(trichloromethyl)-6-                                                                      0.2        6.6                                             (4-methoxystyryl)-s-                                                          triazine                                                                29    3-carboxymethyl-5(3-ethyl-2-                                                                     0.02       13                                              benzothiazolinylidene)-2-                                                     (3-heptyl-4-oxo-2-thio-5-                                                     thiazolinylidene)-4-thia-                                                     zolidone                                                                      diphenyliodonium hexafluoro-                                                  phosphate                                                               30    chlorothioxanthone 0.2        9                                               diphenyliodonium hexafluoro-                                                  phosphate                                                               31    ethyldimethoxy anthracene                                                                        0.02       40                                              diphenyliodonium hexafluoro-                                                  phosphate                                                               32    4,4'-bis(dimethylamino)-benzo-                                                                   0.1        40                                              phenone                                                                 ______________________________________                                    

EXAMPLES 33-39

A stock solution was prepared by mixing 5.13 grams pentaerythritoltetraacrylate, 4.03 grams P-II, 25.5 grams of a 10% by weight solutionof polyvinyl formal in the azeotropic solution of n-propanol and water,119 grams of methylethyl ketone and 1.5 grams of a 20% by weightsolution of triethylamide in the azeotrope. To aliquots of 20 grams ofthis solution were added various photoinitiation systems. Thephotoinitiation systems and amount of each are shown in the followingtable. The solutions were then coated on a grained anodized aluminumsubstrate with a #14 wire wound rod and dried with a heat gun. Theresulting coatings were exposed for 13 seconds to a carbon arc through a21 step sensitivity guide and a 0.5 density filter. The exposed coatingswere developed by wiping with an aqueous solution of 0.63% by weightsodium metasilicate and 0.23% by weight of sodium (loweralkyl)naphthalene sulfonate. The number of solid steps observed aftergumming and inking were recorded. As in previous examples, the higherthe number of steps retained, the greater the sensitivity of thecoating.

    ______________________________________                                                                    Weight   Solid                                    Ex.  Photoinitiation System (Grams)  Steps                                    ______________________________________                                        33   4,4'-bis(dimethylamino)benzophenone                                                                  0.035    0                                        34   4,4'-bis(dimethylamino)benzophenone                                                                  0.035    7                                             diphenyliodonium hexafluorophosphate                                                                 0.070                                             35   7-diethylamino-4-methylcoumarin                                                                      0.035    0                                        36   7-diethylamino-4-methylcoumarin                                                                      0.035    4                                             diphenyliodonium hexafluorophosphate                                                                 0.070                                             37   2,4-bis(trichloromethyl)-6-(4-                                                                       0.070    2                                             methoxystyryl)-s-triazine                                                38   2,4-bis(trichloromethyl)-6-(4-                                                                       0.14     3                                             methoxystyryl)-s-triazine                                                39   4,4'-bis(dimethylamino)benzophenone                                                                  0.035    11                                            2-o-chlorophenyl-4,5-di(m-methoxy                                                                    0.10                                                   phenyl)-imidizole dimer                                                       2-o-chlorophenyl-4,5-diphenyl                                                                        0.10                                                   imidizole dimer                                                               2-mercaptobenzoxazole  0.07                                              ______________________________________                                    

None of these compositions had top coats.

EXAMPLES 40 AND 41

Two additional monomers were evaluated in the compositions of thepresent invention. Two solutions (A and B) were prepared having thefollowing composition:

    ______________________________________                                                            Grams                                                     ______________________________________                                        P-II (64% in methylethyl                                                                            3.12                                                    ketone                                                                        polyvinylformal (10% in the                                                                         7.6                                                     n-propanol-water azeotrope)                                                   P-V (12.9% in n-propanol (62%),                                                                     4.18                                                    isopropanol (10%), and water                                                  (28%))                                                                        dispersion of Pigment Red 48 and                                                                    10.0                                                    polyvinyl formal (10% in the                                                  above azeotrope) in a 2/1 parts                                               by weight ratio resin/pigment                                                 4,4'-bis(dimethylamino)benzo-                                                                       0.19                                                    phenone                                                                       diphenyliodonium hexafluoro-                                                                        0.37                                                    phosphate                                                                     triethylamine (20% by weight                                                                        0.96                                                    in the azeotrope)                                                             n-propanol-water azeotrope                                                                          70.0                                                    ______________________________________                                    

To solution A was added 3.67 grams of pentaerylthritol tetraacrylate andto solution B was added 3.67 grams of tris(2-acryloxyethylisocyanurate). The solutions were then coated onto grained and anodizedaluminum using a number 18 wire wound rod and dried for one minute at65° C. The coated plates were then exposed with a 2 kilowatt diazotypelamp for 2, 5, and 10 seconds in air. The exposed plates were developedby washing with an aqueous solution of 3% sodium metasilicate, 3%n-propanol, 0.3% sodium dodecyl diphenylether disulfonate, and 0.3% ofan alkyl naphthalene sulfonate. The number of solid and ghost stepsremaining after development are given in the following table.

    ______________________________________                                                2 Sec.      5 Sec.      10 Sec.                                       Coating Solid/Ghost Solid/Ghost Solid/Ghost                                   ______________________________________                                        A       4-5         5-7         6-8                                           B       7-8         9-10        9-11                                          ______________________________________                                    

EXAMPLES 42 AND 43

The usefulness of the compositions of the present invention with lowerintensity exposure processes was examined. The compositions as weightpercentages were as follows:

    ______________________________________                                                             Percentage Solids                                                               Solution Solution                                      Component              A        B                                             ______________________________________                                        pentaerythritol tetraacrylate                                                                        43.1     32.3                                          P-II                   23.7     18                                            P-V                    6.25     17.2                                          polyvinyl formal (10% in the azeotrope)                                                              15.2     17.7                                          pigment dispersion (of Example 40)                                                                   3.09     2.8                                           triethylamine (20% in the azeotrope)                                                                 2.15     1.6                                           diphenyliodonium hexafluorophosphate                                                                 4.30     8                                             4,4'-bis(dimethylamino)benzophenone                                                                  2.14     2                                             ______________________________________                                    

Solution A was dried for one minute at 180° F. with a coating weight of200 mg/ft². Solution B was dried with a heat gun at a coating weight of170 mg/ft². The substrate in both cases was grained and anodizedaluminum. A conventional microfilm enlarger was used and the plates wereexposed with between 10 and 30 milliwatts/cm² irradiance by a mercuryxenon lamp through a 21 step sensitivity guide in contact with theplate. Exposure was made in air. The exposed plates were developed bywashing with an aqueous solution of 5.25% metasilicate, 6.37%n-propanol, 8.25% glycerol and 0.075% alkyl naphthalene sulfonate. Theresults are reported below.

    ______________________________________                                                   Exposure Time                                                                             Steps                                                  Plate      Seconds     Solid/Ghost                                            ______________________________________                                        A          2           3-5                                                               4           4-6                                                               6           5-6                                                               8           5-7                                                    B          2           5-7                                                               4           6-8                                                               6           6-8                                                    ______________________________________                                    

When identical plates were imaged (A for 3 seconds and B for 1 second)with line copy and half tones on an aluminum sheet, 10,000 high qualityimpressions were obtained with no image loss.

EXAMPLES 44-50

A standard solution was prepared having the following weight percentagesof ingredients in the n-propanol-water azeotrope:

    ______________________________________                                        pentaerythritol tetraacrylate                                                                      43.2                                                     P-V                  6.35                                                     polyvinyl formal (10% in the                                                                       15.1                                                     azeotrope)                                                                    Pigment Red 48       3.1                                                      triethylamine        2.15                                                     diphenyliodonium hexafluoro-                                                                       4.4                                                      phosphate                                                                     4,4'-bis(dimethylamino)benzo-                                                                      2.2                                                      phenone                                                                       ______________________________________                                    

To seven aliquots of this solution were added 23.5 percent by weight ofthe oligomers P-II and P-VI through P-XI. The solutions were coated ongrained and anodized aluminum using a number 18 wire wound rod and driedfor one minute at 65° C. The dry coatings were exposed in air through a21 step sensitivity guide with a mercury metal halide diazo bulb anddeveloped by wiping with the aqueous developing solution of Example 40.The results are shown in the following table.

    ______________________________________                                                               Steps                                                  Example       Oligomer Solid/Ghost                                            ______________________________________                                        44            P-VI     4-7                                                    45            P-VII    4-7                                                    46            P-VIII   3-6                                                    47            P-IX     4-5                                                    48            P-II     3-6                                                    49            P-X      4-5                                                    50            P-XI     0-2                                                    ______________________________________                                    

The above examples show the effect of varying the ratio of acid groupsto molecular weight of the oligomer. The first two compositions(Examples 44 and 45) had ratios of acid groups to molecular weight ofapproximately 1:4300 and 1:3600 respectively and were more difficult todevelop than preferred and had a tendency to hold the ink on thebackground. A stronger or more vigorous developer could correct thattendency. The oligomer of Example 50 had an acid to molecular weightratio of about 1:750 and developed a little too easily, with much of thephotoreacted material being removed. All compositions were useful andcould be polymerized in air, however. Examples 46 through 49 workedexceptionally well and had a ratio of the number of acid groups tomolecular weight of between about 1:800 and 1:3000, with Example 48having a ratio of about 1:1200. Compositions without any acid groups donot adhere well to the substrate. Development does not differentiatebetween exposed and unexposed areas with both being removedindiscriminately. Compositions without ethylenic unsaturation do notphotoreact and also do not bind to the plate surface.

EXAMPLE 51

A solution was prepared like those in Examples 44-50 using P-XII inplace of the oligomers in the above examples. Coatings were exposed anddeveloped as in Examples 44-50. Only one ghost step and no solid stepswere obtained. Prolonged exposure gave more retained steps.

EXAMPLES 52-57

A solution was prepared for the comparison of different bindermaterials. The solution comprised in parts by weight:

    ______________________________________                                        pentaerythritol tetraacrylate                                                                      41.3                                                     P-II                 22.5                                                     polyvinyl formal     9.95                                                     Pigment Red 48       2.94                                                     triethylamine        2.05                                                     diphenyliodonium hexafluoro-                                                                       4.2                                                      phosphate                                                                     4,4'-bis(dimethylamino)benzo-                                                                      2.1                                                      phenone                                                                       selected binders     14.9                                                     ______________________________________                                    

The binders selected were

    ______________________________________                                        52.      P-V                                                                  53.      low molecular weight hydroxypropyl cellulose                         54.      polyvinyl butyral (MW 38,000-45,000)                                 55.      polyamide (Elvamide.sup.R nylong resin                                        supplied by DuPont Co.)                                              56.      polyvinyl formal                                                     57.      no resin                                                             ______________________________________                                    

The solutions were coated onto salt plates (clear crystals of sodiumchloride), dried, and the infrared spectrum determined. The coatingswere exposed in air to radiation from a 2 kilowatt mercury metal halidediazo bulb for various times at various irradiances. The infraredspectrum was determined after the exposure and the percentage of doublebonds converted by the exposure was calculated on the basis of theabsorption at 810 cm⁻¹. The results appear below.

    ______________________________________                                                     Percentage of Double Bonds                                       Example      Converted at 9 mW/cm.sup.2 Irradiance                            ______________________________________                                        52           35                                                               53           32                                                               54           32                                                               55           27                                                               56           25                                                               57           15                                                               ______________________________________                                    

EXAMPLES 58-69

A solution was prepared for the comparison of different bindermaterials. The solution comprised in parts by weight:

    ______________________________________                                        pentaerythritol tetraacrylate                                                                      43.1                                                     P-II                 23.7                                                     polyvinyl formal     15.0                                                     Pigment Red 48       3.0                                                      triethylamine        2.2                                                      diphenyliodonium hexafluoro-                                                                       4.4                                                      phosphate                                                                     4,4'-bis(dimethylamino)benzo-                                                                      2.2                                                      phenone                                                                       selected polymeric binders                                                                         6.3                                                      ______________________________________                                    

The binders selected were

    ______________________________________                                        58.        P-V                                                                59.        polyvinylpyrolidone                                                60.        polyvinyl formal                                                   61.        copolymer of vinyl chloride (81%) and                                         vinyl acetate (19%)                                                62.        polyvinyl acetate                                                  63.        polyethylene oxide (MW ≅ 4,000,000)                      64.        polymethylmethacrylate (low molecular                                         weight, inherent viscosity ≅ 0.2)                        65.        low molecular weight polyolefin resin                              66.        linear saturated polyester resin                                   67.        thermoplastic aromatic polyurethane                                68.        cellulose acetate butyrate                                         69.        no resin.                                                          ______________________________________                                    

The results of infrared analysis after coating of these compositions asin Examples 52-57 and exposure to 9 milliWatts/cm² irradiance appearsbelow.

    ______________________________________                                                     Double Bond Conversion                                           Example      %                                                                ______________________________________                                        58           30                                                               59           30                                                               60           25                                                               61           25                                                               62           25                                                               63           24                                                               64           23                                                               65           16                                                               66           15                                                               67           15                                                               68           13                                                               69           15                                                               ______________________________________                                    

In examples 52-69, exposure time was 10 seconds.

What is claimed is:
 1. A polymerizable oligomer of the formula ##STR13##wherein E is an ethylenically unsaturated, free radical polymerizablegroup,D is the residue of a polyisocyanate having at least two of itsisocyanate groups reacted to form ##STR14## bonded to E and R, R is theresidue of a polyol having at least a+b hydroxyl groups, the residueformed by removal of hydrogen from the hydroxyl groups, said polyolhaving a number average molecular weight between 90 and 10,000, A is acarboxylic acid containing group, a is a number having an average valuebetween 2 and 20, and b is a number having an average value between 0.3and
 10. 2. The oligomer of claim 1 whereinE is selected from the classconsisting of acryloyloxyalkoxy, methacryloyloxyalkoxy, vinylalkoxy, andallyloxy groups, D is the residue of a diisocyanate, A is selected fromthe group consisting of ##STR15## m is an integer of from 1 to 6inclusive.
 3. The oligomer of claim 2 whereinE is selected from theclass consisting of acryloyloxyalkoxy and methacryloyloxyalkoxy, andsaid oligomer has 2 to 4 ethylenically unsaturated groups selected fromthe class consisting of acryloxy and methacryloxy.
 4. The oligomer ofclaim 3 whereinR is the residue of a polyesterpolyol having a hydroxyequivalent weight between 90 and 4,000.
 5. The oligomer of claim 1wherein said oligomer is represented by the formula: ##STR16## wherein Eis an ethylenically unsaturated free radical polymerizable groupselected from acryloyloxyalkoxy and methacryloyloxyalkoxy,D is theresidue of a diisocyanate having its two isocyanate groups reacted toform ##STR17## bonded to E and R¹, R¹ is the residue formed by theremoval of active hydrogen atoms and hydroxyl groups from oligomericΩ-hydroxy carboxylic acids or the residue formed by the removal ofactive hydrogen atoms and hydroxyl groups from oligomeric diols, R² isthe residue of an aliphatic polyol having the formula R⁵ (OH)_(a+b)after removal of a+b hydrogens from hydroxyl groups and having a valenceof a+b, or the residue of an aliphatic polyol having the formula##STR18## after removal of (a+b-1) hydrogens from hydroxyl groups and R⁵is the residue of an aliphatic polyol radical formed by having the OHgroups of the polyol removed therefrom and having 3 to 10 valencessubstituted with OH groups, R³ is the residue formed by removal of two##STR19## from a dicarboxylic acid, a is a number having an averagevalue of from 2 to 20, and b is a number having an average value of from0.3 to 10,wherein the molecular weight of (R¹ _(a) R² --R¹)_(b) isbetween 200 and 5,000.
 6. The oligomer of claim 1 wherein said oligomeris represented by the formula: ##STR20## wherein R³ is the residueformed by the removal of two ##STR21## from a dicarboxylic acid, R⁴ is Hor CH₃,c is 2 to 5 inclusive, p is a number average value of from 2 to7.7, q is a number average value of from 0.3 to 4, R⁶ is the residueformed by the removal of two isocyanate groups from a diisocyanate, andR⁷ is an organic polyol radical which is the residue of an organicpolyol with at least three hydroxyl groups removed therefrom and havinga molecular weight of from 90 to 10,000.
 7. The oligomer of claim 1,wherein said oligomer is of the formula ##STR22## wherein R³ is theresidue formed by removal of two ##STR23## from a dicarboxylic acid, R⁴is H of CH₃,R⁶ and R⁸ are independently the residues formed by theremoval of two isocyanate groups from a diisocyanate, di is 1 to 6inclusive, e if an average value of 0.5 to 5 inclusive R⁹ is analkanepolyol radical having a valence of h+1 that is the residue of analkanepolyol having h+1 hydroxyl groups removed therefrom, saidalkanepolyol having a molecular weight of from 100 to 10,000, f is aninteger of 1 to 6, and h is an integer of 2 to 8.